Jet fuel additive

ABSTRACT

A METHOD OF REDUCING MANGANESE-CONTAINING DEPOSITS FORMED ON THE SURFACES OF JET ENGINES FROM BURING FUEL CONTAINING ORGANOMANGANESE COMPOUNDS AS A SMOKE REDUCER IS DESCRIBED. THE DEPOSITS ARE MODIFIED BY ADDING A SULFINYL AMINE TO THE ORGANOMANGANESE-CONTAINING FUEL. THE MANGANESE-CONTAINING DEPOSITS ARE THEREBY REDUCED. CYCLOPENTADIENYL MANGANESE TRICARBONYL COMPOUNDS ARE USEFUL ORGANOMANGANESE COMPOUNDS; N-SULFINYL ANILINES ARE USEFUL SULFINYL AMINES.

United States Patent 3,585,012 JET FUEL ADDITIVE George C. Licke, Oxford, Mich., assignor to Ethyl Corporation, New York, N.Y. No Drawing. Filed Dec. 20, 1968, Ser. No. 785,802 Int. C1. C01! 1/24 US. C]. 44-68 11 Claims ABSTRACT OF THE DISCLOSURE A method of reducing manganese-containing deposits formed on the surfaces of jet engines from burning fuel containing organomanganese compounds as a smoke reducer is described. The deposits are modified by adding a sulfinyl amine to the organomanganese-containing fuel. The manganese-containing deposits are thereby reduced.

cyclopentadienyl manganese tricarbonyl compounds are useful organomanganese compounds; N-sulfinyl anilines are useful sulfinyl amines.

BACKGROUND OF THE INVENTION Smoke produced during the operation of a distillate fuel burning engine, such as a jet engine, is undesirable. It contributes to air pollution. It indicates reduced engine efiiciency.

This exhaust smoke may be reduced by adding suitable additives to the fuel. Especially effective additives are certain cyclopentadienyl manganese tricarbonyls, such as (methylcyclopentadienyl)manganese tricarbonyl. US. 2,818,417 provides a thorough list of useful compounds of this type, and includes methods of preparing them. Although use of these manganese additives substantially reduces the exhaust smoke, a secondary problem may arise in some instances. On combustion of the fuel containing the manganese compound, manganese-containing deposits are formed on the engine surface which was contacted by the exhaust products. As With many engine deposits, an effective method of reducing these manganesecontaining deposits is desirable.

SUMMARY OF THE INVENTION A method of reducing manganese-containing deposits formed on the surfaces of jet engines which burn fuel containing organomanganese compounds, which comprises adding to said fuel prior to burning a deposit-reducing amount of a sulfinyl amine in an amount sufficient to reduce the build-up of said manganese-containing deposit.

DESCRIPTION OF PREFERRED EMBODIMENT wherein x is an integer from 1 to 4 inclusive and R is selected from (a) C C alkyl groups,

(b) C C aryl groups,

(c) C C alkenyl groups, and

(d) alkylene amino groups having the formula Patented June 15, 1971 wherein R and R are independently selected from hydrocarbon alkyl groups having from 2 to about 4 carbon atoms, and y is 0 to 6, and burning the fuel in said engine.

Fuel compositions which are used in the preferred method contain 0.025 to about 6.45 grams of manganese per gallon as a cyclopentadienyl manganese tricarbonyl and suflicient sulfinyl amine of Formula I so that the molar ratio of cyclopentadienyl manganese tricarbonylzsulfinyl amine is from about 1:1 to about 3:1; a molar ratio of about 2:1 is preferred. N-sulfinyl aniline and (methylcyclopentadienyl)manganese tricarbonyl in the preferred ratio in the fuel is a most preferred embodiment.

Manganese compounds which are useful as smoke reducers in jet fuels are cyclopentadienyl manganese tricarbonyls having the formula wherein R is a cyclopentadienyl hydrocarbon radical having from 5 to 17 carbon atoms. US. 2,818,417, issued Dec. 31, 1957, contains an extensive disclosure of the type of manganese compounds which are useful. This listing of compounds is incorporated by reference.

(Methylcyclopentadienyl)manganese tricarbonyl is an especially effective smoke reducer.

The concentration of the manganese tricarbonyl in the jet fuels may be varied. Concentrations from 0.025 to about 6.45 grams of manganese per gallon as a cyclopentadienyl manganese tricarbonyl are useful.

By jet fuels, we include distillate hydrocarbons and blends which are useful as fuel for jet engines. These fuels are principally hydrocarbon distillates heavier than gasoline. In other words, they are distillate hydrocarbon fuels having a higher end point than gasoline. They are generally composed of distillate fuels and naphthas and blends of the above, including blends with lighter hydrocarbon fractions. The end point of preferable jet fuels is at least 435 F., and more preferably, greater than 470 F.

Typical jet fuels include JP-3, a mixture of about percent gasoline and 30 percent light distillate having a 90 percent evaporation point of 470 F.; JP-4, a mixture of about 65 percent gasoline and 35 percent light distillate especially designed for high altitude performance; JP-5, an especially fractionated kerosene, and the like.

The N-sulfinyl amines used in the invention are defined by Formula I above. Methods of preparing these compounds are available in the art. A representative method of preparing these compounds is direct treatment of the parent primary amine with thionyl chloride in a suitable solvent. The reaction is illustrated by the following equation:

As the equation illustrates, an N-sulfinyl amine is a derivative of a primary amine in which the two amine hydrogens are replaced by the radical. In general then, the N-sulfinyl derivative of any suitable primary amine can be used as an additive in the practice of this invention.

Preferred N-sulfinyl amines are those in which the R in Formula I above is selected from the groups (a)-(d) listed above. N-sulfinyl amines in which R is a C -C alkyl group include linear, cyclic, and branched alkyl groups with one or more sulfinyl moieties. Representative examples of N-sulfinyl amines are:

N-sulfinyl-n-methylamine, N-sulfinyl-n-octadecylamine, N-sulfinyl-Z-ethyl-n-hexylamine, N-sulfinyl-2,4,4,6,6-pentamethyl-n-heptylamine, N-sulfinyl cyclohexylamine,

N-sulfinyl cyclopentylamine,

3 4 N-sulfinyl cycloctylamine, N-sulfinyl amines where R is the group represented by N-sulfinyl laurylamine, H and the like. R l R Representative examples of N-sulfinyl alkyl amines hav- 1 I 2 ing more than one sulfinyl group are: 5

wherein R R and y are as defined above, are derived N,N, disulfinyl 15 pentanediamine from C C alkylene diamines and polyamines. Repre NN, disulfinyl l,IOdecanediamine, sentatwe examples of these types of N-sulfinyl amines are: N,N',N",N"-tetrasulfiny1-(2,3-methylamine) III 1,4-b11tanediamine, OS=NC:H4N=SO, OS=N-C1H4-NC2H1N=SO N,N,N"-trisulfiny1-1,6,l2-dodecanetriamine, N,N'-disulfiny1-1,IS-Octadecanediamine, and the like. OS:N(C:H1N)4C H1N=SO N-sulfinyl amines wherein R in Formula I is a 0 -0 aryl group can have one or more sulfinyl groups; and R 15 1 can be an unsubstituted aryl group, substituted aryl group, OS:N (C2II4N4)5C2H4N=S0, OS=NC3Hs alkaryl and aralkyl group, mononuclear as well as poly- H H nuclear aryl group. Representative examples of these N- sulfinyl aryl amines are:

N-sulfin l- -na hth lamine, and th like. N-sulfini l- -digheng lamine, Mix ures of N-sulfinyl amme compounds described N-sulfinyl-4-dodecylanili above can also be used in the fuels of the present in- N-sulfinyl-Z,4-didodecylaniline, ventlon. N-sulfinyl-2,4-dimethylamine, The amount of the N-sulfinyl am1ne descrlbed above N- 1fi 1b 1 i which is added to the organomanganese-containing fuel N-su1finyl-e -anthracenylamine, may be varied. It is preferred that sufficient N-sulfinyl N-Sulfinyl-Z-isOpropylaniline, amine is added to the fuel so that the molar ratio of N-sulfinyl-4-0ctadecylaniline, cyclopentadienyl manganese tricarbonylzN-sulfinyl amine N-sulfinyl-2,4,6-triethylaniline, 1S utZil. I I N- 1fi 1 N'. h p h i i The following examples 1llustrate but do not l1m1t et N N' di lfi l 4 4' di h 1di i fuel compositions useful in this invention. N,N,N"-trisulfinyl-1,3,5-benzenetria1nine, Example 1 N,N,N",N-tetrasulfinyl-1,2,4,6-benzene tetramine,

N,N, disulfinyl benzidine, To a JP-S (ASTM-Type A) base fuel was added 2.58

grams/gallon of Mn as (methylcyclopentadienyl)mangagig i i g dlchlorobenzldme nese tricarbonyl and 3.27 grams/ gallon of N-sulfinyl ani- 40 line.

More referred N-sulfin l a l amines are those derived from lovger aryl mononucl ear riionoand diamines having T cyclopentaqlenyl mfmganese t.n.carb.ony1:N'Su1finy1 from 6 to about 18 carbon atoms. Representative examhne molar ratio of thls Composmon 1S amples of these N-sulfinyl aryl amines are: EXAMPLE 2 To a JP5 base fuel were added 2.58 grams/gallon of Mn as (methylcyclopentadienyl)manganese tricarbonyl and 6.54 grams/gallon of N-sulfinyl aniline. N Su1finy1 2 sec buty1aniline he cyclopentadienyl manganese tricarbonyhN-sulfinyl N Su1finyl 6 tert butylanilin, an1l1ne molar ratio of th1s compos1t1on is 1:1.

N-sulfiny1-2,G-dimethylaniline, 5Q EXAMPLE 3 f: To a JP-S base fuel were added 2.58 grams/gallon of N'sulfinylamhne Mn as (methylcyclopentadienyl)manganese tricarbonyl N'sulfinylphenethylamFe and 2.18 grams/gallon of N-sulfinyl aniline.

N'Su1finy1'3'dodecylamhne The cyclopentadienyl manganese tricarbonylzN-sulfinyl N-sulfinyl-2-methylaniline, N-sulfinyl-Z-chloroaniline, N-sulfinyl-4-chloroaniline,

qi p aniline molar ratio of this composition is 3:1. N-sulfinyl-p-amsldlne, N-sulfinyl-o-nitroaniline, EXAMPLE 4 N-sulfinyl-Z,6-diisopropylaniline,

T JP-5 b f l N,N, dislflfinyl o phenylenediamine 0 a ase uel were added 2 58 grams/ gal on of Mn as (methylcyclopentadienyl)manganese tricarbonyl N,N"dlsulfinyl'gmethyl'Piphenylenedlamme 60 and 3.62 grams/ gallon of N-sulfinyl-4-methylaniline. N-S111fi11Yl-2,6idlmethyliflllllllee The cyclopentadienyl manganese tricarbonylzN-sulfinyl N-sulfinyl-3d1methylan1l 1 amine molar ratio of this composition is 2:1. N-sulfinyl-4-dimethylaniline, N-sulfiny1-2,4-di-tert-butylaniline, w EXAMPLE 5 Y 'P'P Y ()0 To a JP-S base fuel are added 1.29 grams/gallon of a d thellke- Mn as (methylcyclopentadienyl)manganese tricarbonyl N-sulfinyl amines Where R m Formula I is an alkenyl and 11.9 grams/gallon of N-sulfinyl 2,6-didodecylaniline. group include monoas well as poly-unsaturated alkenyl The cyclopentadienyl manganese tricarbonyl:N-sulfinyl compounds. Representitive examples of these N-sulfinyl amine molar ratio of this composition is about 1:1. alkenyl amines are N-sulfinyl allylamine, N-sulfinyl oleylamine, N-sulfinyl linoleylamine, N-sulfinyl-4-pente- EXAMPLE 6 y amine, y p y amine, y To a ]P5 base fuel are added 5.19 grams/gallon of 6 dodecenyl 1,12 diamine, N sulfinyl 2 propenyl- Mn as (methylcyclopentadienyl)manganese tricarbonyl amine, and the like. and 15.35 grams/gallon of N-sulfinyl 6-dodecylaniline.

The cyclopentadienyl manganese tricarbonyltN-sulfinyl amine molar ratio of this composition is about 2: 1.

EXAMPLE 7 To a JP-S base fuel are added 2.58 grams/gallon of Mn as (methylcyclopentadienyl)manganese tricarbonyl and 2.9 grams/gallon of N-sulfinyl 2-ethylhexylamine.

The cyclopentadienyl manganese tricarbonyl:N-sulfinyl amine molar ratio of this composition is 3: 1.

Useful jet fuel compositions having the deposit modifying characteristics described below are also prepared (a) by using JP4, JP3, and the like, in place of JP-S in the above examples, (b) by using equivalent amounts of compounds such as N-sulfinyl laurylamine, N-sulfinyl pentylamine, N-sulfinyl octadecylamine, N-sulfinyl 3- pentenylamine, N-sulfinyl linoleylamine, N-sulfinyl finaphthylamine, OS=N(C H C H N:SO, N-sulfinyl 3-nitroaniline, N-sulfinyl N-sulfinyl-p-phenylenediamine, and the like, in place of the N-sulfinyl amines in the above examples.

These jet fuel compositions are prepared by simply blending the required amount of manganese-containing smoke reducer and N-sulfinyl-containing deposit modifier with the base jet fuel. Conventional fuel blending apparatus and techniques are used.

When a jet fuel containing an organomanganese compound as a smoke reducer is burned in a jet engine, a manganese-containing deposit is formed on parts of the engine which come in contact with the burning fuel and/or its combustion products.

Quite unexpectedly, by adding a small amount of an N-sulfinyl amine of Formula I to the fuel before burning, the deposit formed is substantially reduced.

This unexpected deposit-reducing effect of N-sufinyl amines was demonstrated by using the following laboratory procedure. This test procedure was designed to simulate jet engine conditions.

A clean metal test specimen was placed in the exhaust opening of a tubular burner fuel with the control fuel, JP-S containing 2.58 grams/ gallon of manganese as (methylcyclopentadienyl)manganese tricarbonyl. The burner was ignited and the test specimen was exposed to the exhaust stream until a certain amount of fuel was burned. The test specimen was then removed from the exhaust stream and weighed. The amount of deposit was determined by subtracting the weight of the clean metal test specimen from the exposed metal test piece.

This control test specimen was coated with a light tancolored, dense, hard deposit. Analysis of the deposit showed that it contained manganese oxides primarily.

A second clean test specimen was placed in the exhaust opening of the jet burner, now fueled with the fuel composition of Example 1 (]P5+Mn compound-i-N-sulfinyl aniline). The jet burner was ignited and the test piece was exposed to the exhaust stream until an amount of Example 1 fuel equivalent to the control fuel was burned. The coated test piece was then removed from the exhaust stream and weighed. The amount of deposit was obtained by subtracting the weight of the clean test piece from the coated test piece.

Data obtained for these runs is tabulated below.

TABLE 1.-EFFECT OF N-SULFINYL AMINE ON DEPOSIT Percent Amount of deposit Test Fuel composition deposit, mg. reduction 1 .TP5 plus Mn compound 82 2 Example 1 72 12 6 in jet engines. This deposit reduction improves the efficiency and increases the life of the jet engine.

The method and fuels of the present invention are fully described above. It is intended that this invention be limited only within the spirit and lawful scope of the following claims.

I claim:

1-. A method of reducing manganese-containing deposits formed on the surface of a jet engine from burning a fuel containing a smoke-reducing quantity of a cyclopentadienyl manganese tricarbonyl, wherein the cyclopentadienyl radical has up to 17 carbon atoms; which comprises adding to said fuel prior to burning a depositreducing amount of a sulfinyl amine having the formula whcrein x is an integer from 1 to 4 inclusive and R is selected from (a) C C alkyl groups,

(b) Q y-C aryl groups,

(c) C -C alkenyl groups, and

(d) alkylene amino groups having the formula wherein R and R are independently selected from hydrocarbon alkyl groups having from 2 to about 4 carbon atoms, and y is 0 to 6, and burning the fuel containing said cyclopentadienyl manganese tricarbonyl and sulfinyl amine in said engine.

2. The method of claim 1 wherein the amount of said sulfinyl amine present is sufficient to give a molar ratio of said manganese tricarbonyl to sulfinyl amine of from about 1:1 to about 3:1.

3. The method of claim 1 wherein said cyclopentadienyl manganese tricarbonyl is (methylcyclopentadienyl) manganese tricarbonyl.

4. The method of claim 3 is a C -C aryl group and said molar ratio is about 2: 1.

5. The method claim 4 wherein x is an integer from 1 to 2 inclusive.

6. The method of claim 5 wherein R is a C -C mononuclear aryl group.

7. The method of claim 5 wherein said organic compound is N-sulfinyl aniline.

8. Jet fuel containing a smoke reducing quantity of a cyclopentadienyl manganese tricarbonyl, wherein the cyclopentadienyl radical has up to 17 carbon atoms and a deposit reducing amount of a sulfinyl amine having the formula wherein x is an integer from 1 to 4 inclusive and R is selected from (a) C C alkyl groups,

(b) C C aryl groups,

(c) C C alkenyl groups, and

(d) alkylene amino groups having the formula wherein R and R are independently selected from hydorgen alkyl groups having from 2 to about 4 carbon atoms, and y is 0 to 6, such that the molar ratio of said cyclopentadienyl manganese tricarbonyl to said sulfinyl amine is from about 1:1toabout3z1.

9. Jet fuel of claim 8 wherein said cyclopentadienyl manganese tricarbonyl is (methyl-cyclopentadienyl) manganese tricarbonyl.

10. Jet fuel of claim 9 wherein R is C -C aryl group and said molar ratio is about 2:1 and x is an integer 1 to 2 inclusive.

7 8 11. Jet fuel of claim 10 wherein said sulfinyl amine 3,110,577 11/1963 Brown et a1. 44-68 is N-sufinyl aniline. 3,160,592 12/1964 Brown 4468 3,348,932 10/1967 Kukin 4457 References Cited A I UNITED STATES PATENTS D N EL E. WYMAN, Primary Examiner 2,268,384 12/1941 Cloud et a1. 44 s7 YH'SMITHASSStantEXmmer 2,493,284 1/1950 Farkas 44-57 U.S.C1.X.R. 2,737,932 3/1956 Thomas 4468UX 44 72 mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,585,012 Dated June 15, 1371 Inventorfi) George C. Licke It is certified that error appears in the above-identified patent and that: said Letters Patent are hereby corrected as shown below:

In Column 5, line 18, that part of the composition N'sulfinyl'" should read N'-eyclohexyl In Claim 4, line 1, after 5, the phrase wherein R should be added.

Signed and sealed this 12th day of October 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,JR.

ROBERT GOT'I'SCHALK Attesting Officer Acting Commissioner of Patents 

